Agilent and ASTM

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Update on Recent Activities

ASTM – Committees for Refining, Fuels, Petroelum Products

• Global, non-profit, consensus organization • Develop test methods, product specifications, practices, terminology, guides and

classifications • 4 main areas of focus: materials, products, systems and services • Over 130 subcommittees cover specific areas - petroleum, chemicals,

environmental, safety, etc. • 10,000+ standards published each year in 73 volumes • 32,000 members in 100+ countries

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ASTM International

D16 Aromatic

Hydrocarbons & related chemicals

D2 Petroleum products & lubricants

D3 Gas fuels

(natural gas) gas fuels

D32 Catalysts

properties & performance

Agilent Involvement with ASTM • Agilent (HP) and ASTM relationship since the 1960s • Currently 6 Agilent scientists actively participate in ASTM D2 and D16 • Participation includes developing methods, introducing new technology, round robins

• Some important methods Agilent (HP) helped develop

- D4815: oxygenates in gasoline - D5580: aromatics in gasoline - D2887 and D3710 SIMDIS for diesel and gasoline - D7423 trace oxygenates in C2 to C5 hydrocarbons steams

• Some current methods under development with ASTM:

- 2-D Capillary GC method for oxygenated additives in gasoline (D4815 replacement) - Aromatics and methanol in high methanol fuels using heart-cutting 2-D GC - New inlet conditions (MMI) for biodiesel (D6584) - Alternative carrier gases for D5580 (aromatics in gasoline), D4815 (oxygenates in

gasoline), D3606 (benzene/toluene in gasoline), D2887 (SIMDIS for middle distillates)

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New ASTM Developments for Gas Phase Analyses

• New methanol/gasoline blends - methanol easily made from new sources of natural gas (fracking technology) - GC method measures up to 85% methanol in gasoline blends

• 2-D GC method based on Agilent Deans switch application (pub # 5988-9460N)

• Recycled motor oils - recovering used motor oil saves petroleum resources - must meet specifications for fuel and glycol contamination - New D7593 method uses GC with back flush to measure gasoline and

diesel contamination • Agilent helped write GC conditions using 7890 Capillary Flow Technology back flush

- GC Headspace method proposed to measure ethylene glycol in oil • D4291 will remain the primary method to measure ethylene glycol in oil • D4291 uses liquid-liquid extraction followed by GC-FID analysis

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New ASTM Developments for Gas Phase Analyses

• D7845 approved to measure chemical contaminants in marine fuel oil - fuel contaminated with phenols, styrenes, pinenes, alcohols - method developed on Agilent 5977 GC/MS system with CFT back flush - Agilent will participate in 2014 round robin - a new GC-QQQ method under development to measure FAMEs, fatty acids,

bis-phenols and glycerides contaminants in marine fuel

• Gasoline SIMDIS method D3710 using packed columns is withdrawn - D7096 is the new method using capillary columns

• D7798 approved as new Ultrafast SMDIS method

- D2887 equivalent - developed using Agilent LTM column heating technology - Agilent participated in round robin

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Examples of Agilent’s Current Work with ASTM • Gasoline and Biofuels

- Capillary GC version of D3606 under development • Improved separation of benzene from ethanol and butanol gasoline blends

• Uses fluidic switch (Deans switch) with backflush

- Investigation of a new capillary D4815 method • improved oxygenate separation from olefins

- 3-in-1 ASTM Gasoline Solution Using 7890 Large Valve Oven • Configures D3606, D5580 and D4815 on a single instrument

• Diesel Fuels and Biodiesel - D7798 Ultrafast SIMDIS using direct column heating technology – Agilent LTM - Improvements to ASTM D6584 Biodiesel method

• Better performance using Agilent Multimode Inlet

• Alternative GC carrier gas - Response to helium shortages and price increases - Reviewing current ASTM GC methods for capability with nitrogen or hydrogen

• SIMDIS and D4815 methods currently under ballot for nitrogen or hydrogen carrier gas use

- New Agilent 7890 Helium Conservation Module - New Agilent 7890 Hydrogen Sensor

New D3606 Capillary GC Configuration - Improved Separation of Benzene

Jim McCurry

Agilent Technologies

Wilmington, DE USA

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CFT Splitter at Sample Injection Use FID1 signal to determine time toluene elutes from pre-column. This is the back-flush time.

Aux EPC

Pre-column: HP1 30m x 0.25mm x 0.50um Analytical column: Innowax

60m x 0.32mm x 1.00um

UDFS restrictor 0.58m x 0.1mm

S/S Inlet EPC

FID 1

FID 2

P = 40.341 psig

P = 22.375 psig

2.9 mL/min

2.7 mL/min

Toluene Elution Time on Pre-Column Faster & easier back flush set-up with CFT and UDFS restrictor

min 0.5 1 1.5 2 2.5 3 3.5 4

ethanol

benzene

i-C8

MIBK

toluene

Pre-column Restrictor FID1

4.22 min back flush time

CFT Splitter at Back Flush Time (4.22 min)

Aux EPC

Pre-column: HP1 30m x 0.25mm x 0.50um Analytical column: Innowax

60m x 0.32mm x 1.00um

UDFS restrictor 0.58m x 0.1mm

S/S Inlet EPC

FID 1

FID 2

P = 5.033 psig

P = 18.076 psig

-1.2 mL/min

2.0 mL/min

Flow Modifications to Resolve Toluene/i-Butanol

initial Temp 75oC Initial hold 8min ramp 1 5oC/min Temp 2 80oC Hold 2 Until i-BuOH elutes 5min ramp 2 10oC/min Final temp 95oC Final hold until n-butanol elutes

Backflush time (until toluene elutes) 4.23

analytical Flow rate at time 0 2.9 mL/min analyltical Flow rate 0.1min after BF time 2.0 mL/min Pre-column flow rate at time 0 2.7 mL/min

Commercial Pump Gasoline Sample

ethanol

benzene

MIBK

toluene

Better separation of ethanol from benzene compared to D3606 packed column configuration

Comparison of Helium and Nitrogen Carrier Gas Operation for ASTM D4815

Jim McCurry

Agilent Technologies

Wilmington, DE USA

D4815 Configuration

1 2 3

4 5 6 7

8

9 10

S/S EPC

Aux EPC

TCEP column

HP-1 capillary column

FID

split/splitless inlet

variable restrictor

Primary flow

Secondary flow

TCD

Helium Conservation Module Seamlessly integrated onto 7890 GC hardware and software

To Inlet EPCs Purge

He in

N2 in

Flow channel inside the bridge block

Std. Aux EPC

• Built on 5th generation EPC

• Fully controlled by Agilent data systems

• Purge channel prevents cross contamination of gases

• Precise pressure control between tank and GC

• Switch between gases within 15-30min for most detectors

Helium Conservation Module Helium Operation Mode

To GC Inlet

EPC

AUX EPC 1

Nitrogen

0 psig

AUX EPC 3

Purge

10 psig

AUX EPC 2

Helium

80 psig

(< 0.2 mL/min) N2

1 mL/min (out)

Bridge Block

Helium ON at 80 psig, Nitrogen OFF

Helium Conservation Modules Nitrogen Operation Mode

Bridge Block

To GC Inlet

EPC

AUX EPC 1

Nitrogen

80 psig

AUX EPC 3

Purge Vent

10 psig

AUX EPC 2

Helium

0 psig

24.2 mL/min N2

(< 0.2 mL/min) He

1.0 mL/min (out)

Helium OFF, Nitrogen ON at 80 psig

D4815 – Helium and Nitrogen Carrier Gas Operating Conditions

Helium GC Conditions Nitrogen

Col1: TCEP Micropacked 5.0 mL/min (17.8 psi) 5.0 mL/min (16.7 psi)

Col2: PDMS Capillary 3.1 mL/min (14.7 psi) 3.1 mL/min (13.8 psi)

Split Flow 70 mL/min 70 mL/min

TCEP Backflush Time 0.24 min. 0.24 min

TCEP Reset Time 0.84 min. 0.84 min

Valve Oven Temp 60o C 60o C

Column Oven Temp 60o C 60o C

D4815 – Helium and Nitrogen Carrier Gas Calibration of Oxygenates

Helium Carrier Gas Nitrogen Carrier Gas Compound corr (>= 0.99) slope y-int y-int test (<0.1) corr (>= 0.99) slope y-int y-int test (<0.1)

MeOH 1.0000 0.8002 -0.0939 0.01 1.0000 0.7853 -0.0925 0.01

EtOH 1.0000 1.2108 0.0213 0.00 0.9999 1.1989 0.0233 0.00

i-PrOH 1.0000 1.3307 0.0136 0.00 0.9999 1.3149 0.0154 0.00

t-BuOH 1.0000 1.9633 -0.0079 0.00 0.9999 1.9768 -0.0092 0.00

n-PrOH 1.0000 1.6158 -0.0139 0.00 1.0000 1.6293 -0.0158 0.00

MTBE 1.0000 1.7311 0.0276 0.00 0.9999 1.7135 0.0256 0.00

2-BuOH 1.0000 1.6399 -0.0011 0.00 1.0000 1.6569 0.0004 0.00

DIPE 1.0000 1.5954 0.0050 0.00 0.9999 1.5853 0.0010 0.00

i-BuOH 1.0000 1.9322 -0.0141 0.00 0.9998 1.9141 -0.0157 0.00

ETBE 1.0000 1.9712 -0.0582 0.00 0.9998 1.9872 -0.0593 0.00

t-Amyl-OH 1.0000 2.0232 0.0175 0.00 0.9994 2.0061 0.0191 0.00

n-BuOH 1.0000 1.7988 -0.0192 0.00 1.0000 1.7841 0.0009 0.00

D4815 – Helium and Nitrogen Carrier Gas MTBE in Gasoline

4 6 8 10 12 14 16 Min.

MTBE Helium Carrier Gas

Nitrogen Carrier Gas

4 6 8 10 12 14 16 Min.

D4815 – Helium and Nitrogen Carrier Gas Ethanol in Gasoline

Ethanol

Helium Carrier Gas

Nitrogen Carrier Gas

D4815 – Helium and Nitrogen Carrier Gas Results from 3 Gasoline Samples

Gas1 wt% MTBE Gas2 wt% Ethanol Gas3 wt% Ethanol Helium Nitrogen Helium Nitrogen Helium Nitrogen

run1 13.146 13.186 6.007 6.078 10.559 10.466 run2 13.127 13.172 5.983 6.128 10.560 10.578 Avg 13.137 13.179 5.995 6.103 10.560 10.522

r (calc) 0.019 0.014 0.024 0.050 0.001 0.112 r (spec) 0.212 0.212 0.179 0.181 0.253 0.252

Inlet Comparison of ASTM D6584: COC vs. Temperature Programmed Split

Jim McCurry

Agilent Technologies

February 19, 2014

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Inlets With Temperature Program Capability

• Inlet temp programming provides flexibility for injection volume, analysis of thermally labile samples and minimizing inlet discrimination for high molecular Wt components

• Greater sensitivity through large volume injections • Reduce sample preparation steps, resulting in enhanced productivity • Solvent venting and Backflush are possible using auxiliary pressure

source and CFT device

Multimode Inlet (MMI)

Extremely flexible

Split/splitless

Multiple injection

COC Simulation

Can eliminate needle discrimination

Minimal thermal stress on sample

Large volume capability

Standard Techniques

Cold split injection

Cold splitless injection (COC simulation)

Hot split injection

Solvent venting

Stationary phase/solvent venting for focusing

Multimode Inlet Features Hardware • Temperature range of -160C to 450C • Heating @ 15C/sec • Septum/Liner Easily Exchangeable • Injection Modes: Hot S/SL, Cold S/SL, all in pulsed mode, solvent vent mode,

residue removal mode • Support for single stroke injections from 0.1 mL to 250 mL • EPC Compatible with Packed Liners • Compatible with 7890A, 5975C, 7683, CTC Combi PAL

Software • Ten temperature ramps • Solution for solvent vent timing • Fully integrated into ChemStation, MSD ChemStation, EZChrom, MassHunter

New Multimode Inlet Improvements

Standard column nut

Standard 11mm septa

No leaks at liner

Turn-top easy liner exchange

Air plus CO2, N2 cryogenic cooling

Standard liner dimensions

MMI Conditions Used For ASTM D6584

Column: Agilent Select Biodiesel 15 m x 0.32 mm, 0.10 μm (p/n CP9079) Carrier: Helium 5.6 mL/min constant flow Oven: 50°C (hold 1 min), then to 180°C at 15°C/min, then to 230°C at 7°C/min, then to 380°C at 30°C/min (hold 10 min) Injection: MMI Cold-Splitless, Initial temp 88°C for 0.1min, then to 350°C at 250°C/min (hold 1 min) Purge time 1.00min., Purge Flow 9.6ml/min. Detector: FID at 380 °C Sampler: Agilent 7693, 1μL volume injection

Soy B100 Run With MMI

Comparison of Single Lab Precision (r) For MMI and COC Inlet

COC MMI COC MMI COC MMI COC MMI COC MMIRun 1 0.146 0.147 0.25 0.25 0.10 0.10 0.05 0.04 0.230 0.231Run 2 0.146 0.146 0.24 0.25 0.10 0.10 0.05 0.04 0.227 0.231Average 0.146 0.147 0.25 0.25 0.10 0.10 0.05 0.04 0.229 0.231r (calc) 0.000 0.001 0.01 0.00 0.00 0.00 0.00 0.00 0.003 0.000r (spec) 0.024 0.024 0.03 0.03 0.01 0.01 0.02 0.01 0.028 0.041

wt% Glycerol wt% Monoglycerides wt% Diglycerides wt% Triglycerides wt% Total Glycerin

MMI provides same results as COC MMI provides better precision

Summary Agilent and ASTM have a long and successful history for developing new solutions for HPI measurements

Agilent continues to provide strong support and leadership within ASTM community

Agilent works with ASTM members to understand new measurement technologies and incorporate them into the latest methods

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